JP2008081545A - Water-based coloring material and powdery coloring material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-based coloring material comprising fine particles of PIC (polyion complex), having a small average particle diameter, a narrow particle diameter distribution, and excellent preservation stability, and obtained by combining a polymer and a dye; and to provide a powdery coloring material obtained by drying the water-based coloring material. <P>SOLUTION: The water-based coloring material contains (I) a polymer compound having (A) an epoxy resin residue and (B) a cationic hydrophilic polymer segment, and (II) a coloring compound having an anionic group. The water-based coloring material in which the epoxy resin residue (A) part in the polymer compound (I) is in a colloidal shape formed by hydrophobic association in an aqueous medium is preferable, and the powdery coloring material is obtained by drying the colloidal water-based coloring material. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an aqueous coloring material and a powdered coloring material, and more specifically, an aqueous coloring that can be suitably used for various inks such as an aqueous ink such as an ink jet ink, a display member such as a color filter, and an automobile paint. The present invention relates to a material and a powdered coloring material obtained by drying it.

  In recent years, polymers that have oppositely charged charges and dyes have been used as a technique to achieve the water resistance and light resistance of pigments without compromising the variety of colors, the vividness of the colors, and the high saturation. In combination, these are attracted by electrostatic force, and at the same time, stacking is caused by the interaction between the π-electron planes of the dye molecules that have spread widely, and a method of forming a polyion complex (PIC) has been known. The PIC thus obtained has crystallinity, is a means capable of preventing bleeding, which is a weak point of the dye, and improving light resistance, water resistance, gas resistance, and the like. For example, when both aqueous solutions of a cationic polymer and an anionic dye are mixed, the cationic portion and the anionic portion cancel each other and become hydrophobic, so that a water-insoluble PIC solid can be obtained ( For example, refer nonpatent literature 1.).

  However, since the water-insoluble PIC solid proposed in Non-Patent Document 1 easily precipitates in water, when this is used as an aqueous coloring material, a dispersion synthesized separately as in the case of pigment dispersion. It is necessary to add a resin and adsorb the resin while pulverizing it with a strong shearing force, which requires a large capital investment and unnecessary power, and a solution is required.

  As means for solving the above problems, for example, from a block copolymer or graft copolymer having an ionic hydrophilic polymer unit and a nonionic hydrophilic polymer unit, and a coloring compound having an ionic group An aqueous coloring material has been proposed (see, for example, Patent Document 1).

  Although a dispersion having a small average particle diameter is obtained by the method proposed in Patent Document 1 and an aqueous coloring material can be obtained without using the above-described apparatus, coarse particles considered to be due to fusion between PICs. Because it occurs, its particle size distribution range is wide, and there are few parts with the appropriate particle size when used as a coloring material, so the yield is poor, and the factors that cause blisters when coating and coating This may cause clogging of the head portion of the apparatus, and furthermore, the fusion occurs during storage, so that the storage stability is poor, and there is still a problem for practical use.

C. F. J. et al. Faul, M.M. Antonietti, Chem. Eur. J. et al. , 2002, 12, 1276-2768. JP 2005-036039 A

  In view of the above situation, the problem to be solved by the present invention is an aqueous coloring material composed of fine particles of PIC combining a polymer and a dye, the average particle size of which is small and the particle size distribution is narrow, and the storage stability is excellent. Another object of the present invention is to provide a powdered coloring material obtained by drying it.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies. As a result, fine particles having a specific hydrophobic core portion and a shell portion made of a cationic hydrophilic polymer segment in an aqueous medium. The present invention has been completed by finding that fine particles composed of a polyion complex having a narrow particle size distribution range can be obtained by combining a polymer compound capable of forming an anionic group and a coloring compound having an anionic group.

  That is, the present invention contains a polymer compound (I) having an epoxy resin residue (A) and a cationic hydrophilic polymer segment (B), and a coloring compound (II) having an anionic group. It is an object of the present invention to provide an aqueous coloring material and a powdered coloring material obtained by drying the aqueous coloring material.

  According to the present invention, it is possible to provide an aqueous coloring material composed of PIC which is excellent in water resistance, light resistance, coloring property, dispersion stability and storage stability and has a narrow particle size distribution width. The water-based coloring material solves the respective problems of dyes and pigments, is easy to handle, and can be suitably used for ink-jet inks, water-based paints, printing water-based inks, paints, and the like. . Moreover, it can use suitably also for a photo-alignment film | membrane, a color filter etc. as a raw material relevant to an optical device. Furthermore, the aqueous coloring material of the present invention is stabilized in a colloidal form in which the hydrophobic portions of the polymer compound are associated with each other in the aqueous medium to form the core portion, and the hydrophilic portion is the shell portion. By drying this, a powdery coloring material can be easily obtained. This coloring material is excellent in redispersibility in an aqueous medium, and can be suitably used for application to an aqueous paint or the like.

  The aqueous coloring material of the present invention comprises a polymer compound (I) having an epoxy resin residue (A) and a cationic hydrophilic polymer segment (B), and a coloring compound (II) having an anionic group. It is characterized by containing.

[Epoxy resin residue (A)]
The epoxy resin residue (A) in the polymer compound (I) used in the present invention has hydrophobicity, and is hydrophobically bonded to each other between molecules and / or molecules of the polymer compound (I) in an aqueous medium. It is a structure necessary for forming a hydrophobic core part, and has skeletons derived from various epoxy resins. The residue (A) is bonded to a cationic hydrophilic polymer segment (B) described later via an epoxy group or a hydroxyl group of an epoxy resin used as a raw material. The epoxy resin that can be used as a raw material is not particularly limited, but a bisphenol-type epoxy resin can be obtained because a more stable aqueous coloring material (aqueous dispersion) can be obtained and industrial availability is easy. It is preferable to use a naphthalene type tetrafunctional epoxy resin and a tetraphenylolethane type epoxy resin, and it is particularly preferable to use a bisphenol A type epoxy resin and a naphthalene type tetrafunctional epoxy resin. The number average molecular weight of the epoxy resin residue (A) in the polymer compound (I) is preferably in the range of 300 to 10,000, and more preferably in the range of 500 to 3,000. In addition, it is preferable in that an aqueous coloring material having a small particle diameter can be obtained.

  The above-mentioned epoxy resin has a plurality of epoxy groups per molecule. However, prior to bonding with the cationic hydrophilic polymer segment (B), the oxirane ring in the epoxy group is partially opened beforehand. It may be used in a ring.

  Examples of the substance for opening such an oxirane ring include various alcohols, phenols, secondary amines, etc., and examples thereof include aliphatic alcohols having 1 to 20 carbon atoms, and substituents on aromatic rings. Phenols that may be substituted, phenylphenols that may have a substituent on the aromatic ring, various dialkylamines such as dimethylamine, diethylamine, dibutylamine, dihexylamine, etc. It is preferable to appropriately adjust the type and amount of use according to the introduction method and introduction ratio of the cationic hydrophilic polymer segment (B) to the polymer compound (I).

[Cationic hydrophilic polymer segment (B)]
The cationic hydrophilic polymer segment (B) in the polymer compound (I) used in the present invention is a polymer chain having a cationic group, and a coloring compound (II) having an anionic group described later and This segment is necessary for ionic bonding, whereby the coloring compound (II) can be immobilized in the polymer compound (I) or the aggregate of the polymer compound (I). Examples of the cationic group include those obtained by protonating or quaternizing a nitrogen atom contained in a primary amine, secondary amine, tertiary amine, pyridine ring or the like.

  Examples of the cationic hydrophilic polymer segment (B) include those obtained by cationizing a segment made of a polymer such as polyethyleneimine, polyvinylamine, polyallylamine, and polyvinylpyridine, and among these, more stable. From the viewpoint of obtaining a water-based coloring material (aqueous dispersion), it is preferable that a segment made of polyethyleneimine is cationized. Examples of the cationization method include protonation with hydrochloric acid and the like and quaternary chlorination with iodomethane and the like.

  The molecular weight of the segment (B) is preferably in the range of 100 to 60,000 from the viewpoint of obtaining particles having a small particle size and high crystallinity, and particularly 1, It is preferable that it exists in the range of 000-30,000. Further, the polymerization degree of the polymer constituting the cationic hydrophilic polymer segment (B) is preferably in the range of 3 to 1,000 for the same reason.

  Further, all the monomer units forming the cationic hydrophilic polymer segment (B) may not be cationized, and within 50 mol% or less, preferably 30 mol% or less of all units, Sex units may be included randomly.

  For example, as a hydrophilic monomer used as a raw material for the polymer forming the segment, a nonionic unit is obtained by a method in which a cationizable monomer and a nonionic monomer are used in combination, and these are copolymerized and then cationized. Can be introduced.

  Examples of the nonionic unit include N-acetylethyleneimine, N-formylethyleneimine, N-propionylethyleneimine, N-acetylvinylamine, N-formylvinylamine, N-acetylallylamine, N-formylallylamine and the like. Amides, allylamines, vinylamines, reaction products of ethyleneimines with acid halides such as benzoyl chloride, reaction products of lactones such as β-butyrolactone, lactide, phenyl isocyanate, hexyl isocyanate, etc. The unit which consists of a reaction product etc. with isocyanate of this can be mentioned.

  When the cationic hydrophilic polymer segment (B) is a segment made of polyethyleneimine, for example, after living polymerization of oxazolines to obtain polyoxazoline, 50 mol% or more thereof is hydrochloric acid or water. By hydrolysis using an aqueous sodium oxide solution or the like, a segment containing a cationized (hydrochlorinated) ethyleneimine unit and a nonionic oxazoline unit can be obtained.

[Shape of polymer compound (I)]
The shape of the polymer compound (I) used in the present invention is not particularly limited, and any shape such as a linear shape, a star shape, or a hyperbranched shape can be used. You may mix and use. Furthermore, two or more types of polymer compounds (I) having different shapes can be used in combination. In addition, for example, those obtained by chemically bonding polymers having different shapes such as a linear epoxy resin residue (A) and a star-shaped cationic hydrophilic polymer segment (B) can be used.

  The water-based coloring material of the present invention has a cationic hydrophilic polymer segment (B) because the hydrophobic epoxy resin residue (A) and the cationic hydrophilic polymer segment (B) are directly chemically bonded. ) And a coloring compound (II) having an anionic group to be described later, a hydrophobic PIC part is formed in the vicinity of the epoxy resin residue (A), so that the average particle size is stable and small. Fine particles composed of PIC having a narrow diameter distribution can be obtained.

  The polymer compound (I) used in the present invention contains the epoxy resin residue (A) and the cationic hydrophilic polymer segment (B) as described above. The number average molecular weight of the polymer compound (I) is preferably in the range of 500 to 50,000, particularly 3,000 to 40,000 from the viewpoint of obtaining a small diameter and a narrow distribution width. It is preferable that Also, the weight average molecular weight is preferably in the range of 500 to 100,000 for the same reason, and particularly preferably in the range of 3,000 to 80,000.

  Further, when the mass of the epoxy resin residue (A) in the polymer compound (I) is Wa and the mass of the cationic hydrophilic polymer segment (B) is Wb, Wa / (Wa + Wb) = 0.03. When the ratio is ˜0.8 (mass ratio), an aqueous coloring material having a good particle size distribution and a powdered coloring material obtained by drying it can be obtained. In particular, Wa / (Wa + Wb) = 0. A range of 05 to 0.3 (mass ratio) is preferable because the average particle size is small and the storage stability is excellent.

[Method for Producing Polymer Compound (I)]
The polymer compound (I) used in the present invention is not particularly limited as long as it has the above-described constituent components. As a method for easily synthesizing a polymer compound as designed, for example, (i) an epoxy resin is reacted with a hydroxyl group-containing compound to open an oxirane ring, and the hydroxyl group produced at this time is tosylated to polymerize. Grants starting ability. Using the obtained compound as a polymerization initiator, a monomer such as oxazoline serving as a precursor of a cationic hydrophilic polymer segment is polymerized to obtain a polymer compound. Thereafter, hydrolysis of the polyoxazoline moiety using hydrochloric acid, aqueous sodium hydroxide, or the like, and protonation of the nitrogen atom in the obtained linear polyethyleneimine chain, to obtain the desired polymer compound. (Ii) a method of reacting an epoxy resin with a hydrophilic polymer having a functional group capable of reacting with a hydroxyl group or an epoxy group in the epoxy resin and having a cationizable site such as an amino group Can be mentioned. In particular, when the latter method is used and a polyfunctional amine is used, a part of the oxirane ring in the epoxy resin used in advance is opened with various reactive compounds such as a hydroxy compound to thereby functionalize the oxirane ring. It is preferable to take measures to reduce the concentration and prevent the formation of a gel-like product insoluble in water.

[Dispersion of polymer compound (I)]
The polymer compound (I) used in the present invention forms an O / W type dispersion in a substantially aqueous medium. Since this particle size is often reflected in the particle size of the dispersion of the aqueous coloring material, reducing the particle size of the polymer compound (I) reduces the particle size of the aqueous coloring material, and thus powder coloring. It is important from the point of manufacturing the material. Therefore, when preparing the dispersion of the polymer compound (I), it is preferable to perform an operation for reducing the particle size such as ultrasonic dispersion treatment or high-pressure dispersion treatment.

[Coloring Compound (II) Having Anionic Functional Group]
The coloring compound (II) having an anionic functional group used in the present invention is not particularly limited and is a general compound having a salt structure of an acidic functional group such as a sulfonate structure or a carboxylate structure. Any compound can be used. Classifying this mainly includes acid dyes, acid mordant dyes, direct dyes, reactive dyes and the like. Among these, a compound containing a sulfonic acid alkali metal salt or a carboxylic acid alkali metal salt portion is preferable as the coloring compound (II) used in the present invention.

  In addition, examples of compounds exhibiting particularly excellent dispersion stability in the present invention include compounds in which the coloring compound (II) having an anionic group has a fluorine atom or a bulky hydrophobic functional group. Examples of the bulky hydrophobic functional group include an alkylphenyl group which may have a substituent and a phenoxyphenyl group which may have a substituent. The coloring compound (II) having an anionic group may be one having two or more of the above functional groups, or one having a plurality of different functional groups.

  The coloring compound (II) having an anionic functional group is generally called a dye, and is exemplified by a color index number. I. Acid Black 1, 2, 3, 7, 24, 26, 29, 31, 48, 50, 51, 52, 58, 60, 62, 63, 64, 67, 72, 76, 77, 94, 107, 108, 109, 110, 112, 115, 118, 119, 121, 122, 132, 139, 140, 155, 156, 157, 158, 159, 182, 191, 194, C.I. I. Food Black 2, C.I. I. Direct Black 17, 19, 22, 32, 35, 38, 51, 56, 62, 71, 74, 75, 77, 94, 105, 106, 107, 108, 112, 113, 117, 118, 132, 133, 146, 154, 168, 171, 195, 200, C.I. I. Reactive black 1, 3, 4, 5, 6, 8, 9, 10, 12, 13, 14, 18, 31, and hydrolysates thereof can be used.

  Examples of blue dyes include C.I. I. Acid Blue 1, 7, 9, 15, 22, 23, 25, 27, 29, 40, 41, 43, 45, 54, 59, 60, 62, 72, 74, 78, 80, 82, 83, 90, 92, 93, 100, 102, 103, 104, 112, 113, 117, 120, 126, 127, 128, 129, 130, 131, 138, 140, 142, 143, 151, 154, 158, 161, 166, 167, 168, 170, 171, 182, 183, 184, 187, 192, 199, 202, 203, 204, 205, 229, 234, 236, 249, C.I. I. Direct Blue 1, 2, 6, 15, 22, 25, 41, 71, 76, 77, 78, 80, 86, 87, 90, 98, 106, 108, 120, 123, 158, 160, 163, 165, 168, 192, 193, 194, 195, 196, 199, 200, 201, 202, 203, 207, 225, 226, 236, 237, 246, 248, 249, C.I. I. Reactive Blue 1, 2, 3, 4, 5, 7, 8, 9, 13, 14, 15, 17, 18, 19, 20, 21, 25, 26, 27, 28, 29, 31, 32, 33 , 34, 37, 38, 39, 40, 41, 43, 44, 46, and hydrolysates thereof.

  Examples of the red dye include C.I. I. Acid Red 1, 6, 8, 9, 13, 14, 18, 26, 27, 32, 33, 35, 37, 42, 49, 50, 51, 52, 57, 75, 77, 80, 82, 83, 85, 87, 88, 89, 92, 93, 94, 95, 97, 98, 106, 111, 114, 115, 117, 118, 119, 129, 130, 131, 133, 134, 138, 143, 145, 154, 155, 158, 168, 180, 183, 184, 186, 194, 198, 209, 211, 215, 252, 252, 254, 262, 265, 274, 282, 287, 289, 303, 306, 317, 320, 321, 322, 337, 356, C.I. I. Direct Red 1, 2, 4, 9, 11, 13, 17, 20, 23, 24, 28, 31, 33, 37, 39, 44, 46, 62, 63, 75, 79, 80, 81, 83, 84, 89, 95, 99, 113, 197, 201, 218, 220, 224, 225, 226, 227, 228, 229, 230, 231, C.I. I. Reactive Red 1, 2, 3, 4, 5, 6, 7, 8, 11, 12, 13, 15, 16, 17, 19, 20, 21, 22, 23, 24, 28, 29, 31, 32 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 46, 49, 50, 58, 59, 63, 64, 180 and their hydrolysates, food red 1 , 6, 11, 13, 17 and the like.

  Examples of yellow dyes include C.I. I. Acid Yellow 1, 2, 3, 7, 11, 17, 19, 23, 25, 29, 36, 38, 40, 42, 44, 49, 59, 61, 65, 70, 72, 73, 75, 76, 78, 98, 99, 104, 110, 111, 127, 131, 135, 142, 155, 162, 165, 183, 184, 194, C.I. I. Direct yellow 1, 8, 11, 12, 24, 26, 27, 33, 39, 44, 50, 85, 86, 87, 88, 89, 98, 106, 110, 132, 142, 144, 173, 194, C. I. Reactive yellow 1, 2, 3, 4, 6, 7, 11, 12, 13, 14, 15, 16, 17, 18, 22, 23, 24, 25, 26, 27, 37, 42 and their water Decomposition product, C.I. I. Food yellow 3, 4, 6, 7, 8, 9, etc. can be mentioned.

  In addition, C.I. I. Acid Violet 9, 15, 31, 34, 41, 43, 48, 49, 51, 66, 126, C.I. I. Direct violet 107, C.I. I. Acid Orange 7, 10, 20, 24, C.I. I. Direct Orange 22, C.I. I. Acid Brown 13, 27, 103, 126, 237, 289, 362, C.I. I. Acid green 1, 3, 5, 9, 16, 25, 27, 36, 40, 41, 44, 81 can also be used.

  In addition, pigment molecules with functional groups that can easily generate negative ions such as sulfonic acid, such as tetrasodium salt of copper phthalocyanine tetrasulfonate and quinacridone sulfonate, and raw materials for some lake pigments Those having low hydrophilicity such as transition metal complexes using various organic dyes can be preferably used.

[Aqueous coloring material]
As the use ratio of the polymer compound (I) and the colorable compound (II), the colorant compound relative to the number of moles of cations in the cationic hydrophilic polymer segment (B) in the polymer compound (I) ( II) The value represented by the ratio of the number of moles of anions (anion / cation) is usually 0.05 to 0.95, and 0.05 to 0.5 from the point that a more stable PIC is obtained. It is preferable that it is 0.05-0.3 especially. In addition, when it is difficult to calculate the molecular weight because the coloring compound (II) forms a complex, the use ratio of the polymer compound (I) and the coloring compound (II) is adjusted by the mass ratio. In this case, the colorant compound (II) / polymer compound (I) is preferably in the range of 0.05 / 1 to 6/1 (mass ratio). A range of 5/1 to 4/1 is preferable.

  In addition, the sum of the number of cationized basic groups and non-cationized basic groups in the polymer compound (I) is x (equivalent), and the number of coloring compounds (II) having an anionic group is determined. When y (equivalent) is set, the value of x / y is preferably in the range of 0.2 to 5, and more preferably in the range of 0.5 to 1.5. When the value is larger than this, the number of the coloring compound (II) having an anionic group contained in the polymer compound (I) becomes very small, resulting in faint coloring or the obtained aqueous coloring. Since the crystallinity of the material is lowered, color fastness and light resistance when used as a coloring material may be lowered. On the other hand, when the value is smaller than this, the amount of the coloring compound (II) having an anionic group becomes too large, and it is not sufficiently fixed in the PIC, and the color fastness and light resistance when used as a coloring material. May be low.

As a quantification method regarding the ratio of the polymer compound (I) and the colorable compound (II) in the obtained aqueous coloring material, for example, a method for determining the abundance ratio of functional groups by elemental analysis, A method of comparing the amount used and the amount of non-volatile content after being dried at 150 ° C., separately obtaining the concentration of the coloring compound (II) by a visible light absorption spectrum, etc., and calculating from these values, alkali The dispersion can be decomposed by a method such as a method of measuring by ¹ H-NMR and calculating the ratio from each typical peak intensity.

[Method for producing aqueous coloring material]
The method for producing the aqueous coloring material of the present invention is not particularly limited, and an operation in which the aqueous solution of the polymer compound (I) and the aqueous solution of the coloring compound (II) having an anionic group are combined and stirred. Alternatively, it can be produced by performing two operations of vibrating sequentially, alternately or simultaneously, but it is preferable to combine them while performing a stirring operation. By mixing together while stirring, the hydrophobic polyion complex formed by the cationic part in the polymer compound (I) and the anionic part in the coloring compound (II) does not become a large mass, and a fine dispersion It becomes easy to make.

  As the operation for combining the two kinds of aqueous solutions, the aqueous solution of the polymer compound (I) is added to the aqueous solution of the color compound (II), and the aqueous solution of the color compound (II) is the aqueous solution of the polymer compound (I). Or both of them may be added to the third container, and other organic solvents and polymers other than water can be added within a range not impairing the effects of the present invention. .

  Examples of the purpose of adding the other organic solvents and polymers include viscosity adjustment, adjustment of rheological properties, permeability to paper and various surfaces, adjustment of solubility, and the like, and inhibition of the formation of coarse particles. Thus, the particle size distribution width may be narrowed or the dispersion stability may be improved.

  Examples of organic solvents that can be used include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, isopropyl acetate and methyl acetate, carbonates such as ethylene carbonate and propylene carbonate, methanol, ethanol, ethylene glycol, Alcohols such as glycerin and polyvinyl alcohol, cyclic or non-cyclic ethers such as tetrahydrofuran (THF), dioxane, diethylene glycol, triethylene glycol and triethylene glycol monobutyl ether, cyclic such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone Examples include acyclic amides, sulfoxides such as dimethyl sulfoxide, pyridine, dimethylimidazolidinone, and methylene chloride. Rukoto can be.

  Examples of polymers that can be used include polyether-based (co) polymers such as polyethylene glycol, polypropylene glycol, and polyethylene glycol-polypropylene glycol copolymers, and partially hydroxyl group-protected polyvinyls. Examples thereof include poly (meth) acrylic acid and esters and / or amides mainly composed of alcohols, (meth) acrylic acid and esters or amides thereof.

  It is preferable that stirring of the dispersion obtained by the above operation is continued for a while after mixing. By carrying out such “ripening operation”, the particle size of the resulting dispersion (fine particles) is reduced, the dispersion stability is improved, and it is prevented from fusing and becoming larger when stored for a long time. An effect is obtained.

  In order to further reduce the particle size of the obtained dispersion, it is also preferable to perform ultrasonic dispersion treatment, high-pressure homogenizer treatment, or the like.

  In the mixture obtained above, the coloring compound (II) that has not been incorporated into the dispersion can be removed by a technique such as dialysis or ultrafiltration.

  The aqueous coloring material of the present invention has a core portion formed by hydrophobic association of an epoxy resin residue portion in an aqueous medium, and has a colored hydrophobic association portion around the core portion. By covering with a cationic hydrophilic polymer that does not form an ion complex with the coloring compound (II), it has good water dispersibility without using other dispersants, and further hydrophobic association It is a colloidal particulate water-based coloring material that shows good colorability. In the hydrophobic association part, the coloring compound (II) having a large number of anionic groups is formed by ionic bonding between the coloring compound (II) having an anionic group and the cationic hydrophilic polymer segment (B). Are concentrated along the chain of the polymer compound (I). In the concentrated state, strong π-π stacking occurs between the coloring compound (II) molecules having an anionic group, and the coloring compound (II) is not molecularly dispersed but has a certain regular association structure. Easy to form. Therefore, the obtained coloring material has excellent water resistance and light resistance.

  As the particle size of the colloidal aqueous coloring material, the degree of polymerization of the polymer compound (I) used and the composition of the cationic hydrophilic polymer segment (B) in the polymer compound (I) are adjusted. The particle size tends to increase as the degree of polymerization increases or as the content of the cationic hydrophilic polymer segment (B) increases. The degree of polymerization and the composition of segment (B) need to be adjusted as appropriate depending on the type and structure of other constituents (epoxy resin residues) of polymer compound (I) to be used. In order to obtain an aqueous coloring material, the average particle size is preferably controlled in the range of about 20 nm to 5 μm, and in particular, it is preferably controlled in the range of 100 nm to 1 μm from the viewpoint of excellent storage stability. The aqueous coloring material can be easily controlled within this range.

  Such a colloidal particulate aqueous coloring material can be made into a powdery coloring material that is easy to handle by removing the aqueous medium as a dispersion medium and drying it. The method for removing the aqueous medium is not particularly limited. For example, the aqueous medium can be easily evaporated by heating to 50 to 120 ° C. Moreover, the ratio of solid content can also be made high by the method of using an evaporator and a thin film distillation apparatus, and the method of performing operations, such as ultrafiltration. When the powdered coloring material obtained is returned again to the aqueous medium, it can be easily dispersed without any other dispersant.

  Thus, the aqueous coloring material of the present invention not only has the same coloring power when compared with a coloring compound (dye) in which the molecule is in an isolated state by taking the form of a polyion complex dispersion, Remarkably long endurance time and fastness to coloring against water and organic solvents can be provided. In addition, the particle size can be easily controlled, and it has good dispersibility without using a dispersant, and is excellent in water resistance and light resistance. Therefore, the water-based coloring material of the present invention can be suitably used for ink-jet inks, water-based paints, printing water-based inks, paints and the like. Moreover, it can use suitably also for a photo-alignment film | membrane, a color filter etc. as a raw material relevant to an optical device.

  Hereinafter, the present invention will be described in more detail with reference to examples. Unless otherwise specified, “%” represents “mass%”.

Synthesis example 1
Bisphenol A type epoxy resin EPICLON AM-040-P (Dainippon Ink Chemical Co., Ltd., epoxy equivalent 933) 18.7 g (20 m equivalent), 4-phenylphenol 1.28 g (7.5 mmol), 65% ethyl acetate Triphenylphosphonium ethanol solution 0.26 ml (0.12 mol%) and N, N-dimethylacetamide 50 ml were mixed and reacted at 120 ° C. for 6 hours in a nitrogen atmosphere. After standing to cool, it was dropped into 150 ml of water, and the resulting precipitate was washed twice with methanol and then dried under reduced pressure at 60 ° C. to obtain a monofunctional epoxy resin. The yield of the obtained product was 19.9g.

As a result of measuring ¹ H-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) and considering the integration ratio of epoxy groups, 0.95 oxirane rings remain in one molecule of bisphenol A type epoxy resin, and it is monofunctional. It was confirmed that this was an epoxy resin.

  A monofunctional epoxy resin (3.0 g) obtained by the above synthesis, 7.5 g of branched polyethyleneimine (manufactured by Aldrich, molecular weight 25,000), 30 ml of acetone and 30 ml of methanol were stirred at 50 ° C. for 2 hours in a nitrogen atmosphere. While reacting. After completion of the reaction, a small amount of water was added to the resulting mixture, and then acetone and methanol were removed under reduced pressure at 40 ° C. to obtain a polymer compound (I-1) having a bisphenol A type epoxy resin-polyethyleneimine structure. An aqueous solution was obtained.

  The number average molecular weight of the epoxy resin residue (A) of the obtained polymer compound (I-1) is about 1900, and the number average molecular weight of the cationic hydrophilic polymer segment (B) is about 25,000. When the mass of the epoxy resin residue in the compound (I-1) was Wa and the mass of the cationic hydrophilic polymer segment was Wb, Wa / (Wa + Wb) = 0.71.

Synthesis example 2
Naphthalene-type tetrafunctional epoxy resin EPICLON HP-4700 (Dainippon Ink Chemical Co., Ltd., epoxy equivalent 158) 7.9 g (50 m equivalent), 4-phenylphenol 5.82 g (31.3 mmol), 65% ethyl acetate tri A phenylphosphonium ethanol solution (0.21 ml, 0.1 mol%) and N, N-dimethylacetamide (40 ml) were mixed and reacted at 120 ° C. for 6 hours in a nitrogen atmosphere. After standing to cool, it was dropped into 150 ml of water, and the resulting precipitate was washed twice with methanol and then dried under reduced pressure at 60 ° C. to obtain 15.5 g of a monofunctional epoxy resin.

As a result of measuring the ¹ H-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) and considering the integration ratio of the epoxy groups, 0.98 oxirane rings remain in one epoxy resin molecule, and the monofunctional epoxy resin It was confirmed that.

  Monofunctional epoxy resin 2.1g obtained from the above synthesis, branched polyethyleneimine (manufactured by Aldrich, molecular weight 25,000) 8.4g, acetone 30ml and methanol 30ml were stirred at 50 ° C for 2 hours under nitrogen atmosphere. While reacting. After completion of the reaction, a small amount of water was added to the reaction mixture, acetone and methanol were removed under reduced pressure at 40 ° C., and an aqueous solution of a polymer compound (I-2) having a naphthalene type tetrafunctional epoxy resin-polyalkyleneimine structure Got.

  The number average molecular weight of the epoxy resin residue (A) of the obtained polymer compound (I-2) is about 1100, and the number average molecular weight of the cationic hydrophilic polymer segment (B) is about 25,000. When the mass of the epoxy resin residue in the compound (I-2) is Wa and the mass of the cationic hydrophilic polymer segment is Wb, Wa / (Wa + Wb) = 0.80.

Example 1
100 mg of the polymer compound (I-1) obtained in Synthesis Example 1 was dissolved in 0.90 g of ion-exchanged water, and this was adjusted to pH 3 with 5N hydrochloric acid. To this, an aqueous solution in which 100 mg of red dye (CI Acid Red No. 18: manufactured by Tokyo Chemical Industry Co., Ltd.) was previously dissolved in 4.77 g of ion-exchanged water was dropped. Here, the molar ratio of the anionic group in the red dye as the coloring compound to the amine unit in the polymer compound (I-1) was 30.0%. This was further stirred at room temperature for 12 hours, placed in a dialysis membrane (manufactured by Sanko Pure Chemical Industries, Ltd.), and dialyzed for 5 days in pure water while exchanging water. The obtained particles were 150 nm when the particle size was measured using FPAR1000 (manufactured by Otsuka Electronics Co., Ltd.). Since the ratio of the 90% particle size to the 10% particle size was 2.30, it was confirmed that the particles were PIC dispersion fine particles having a narrow particle size distribution.

Example 2
100 mg of the polymer compound (I-2) obtained in Synthesis Example 2 was dissolved in 0.90 g of ion-exchanged water, and this was adjusted to pH 3 with 5N hydrochloric acid. An aqueous solution in which 100 mg of red dye (CI Acid Red No. 18: manufactured by Tokyo Chemical Industry Co., Ltd.) was previously dissolved in 4.77 g of ion-exchanged water was added dropwise thereto. Here, the molar ratio of the anionic group in the red dye, which is a coloring compound, to the amine unit in the polymer compound (I-1) was 26.7%. The particle diameter of the fine particles obtained in the same manner as in Example 1 was measured and found to be 164 nm. Since the ratio of the 90% particle size to the 10% particle size was 1.91, it was confirmed that the particles were PIC dispersion fine particles having a narrow particle size distribution.

Example 3
100 mg of the polymer compound (I-2) obtained in Synthesis Example 2 was dissolved in 0.90 g of ion-exchanged water, and this was adjusted to pH 3 with 5N hydrochloric acid. To this was added dropwise an aqueous solution in which 100 mg of yellow dye (CI Acid Yellow No. 17: manufactured by Kanto Chemical Co., Ltd.) was previously dissolved in 4.77 g of ion-exchanged water. Here, the molar ratio of the anionic group in the yellow dye as the coloring compound to the amine unit in the polymer compound (I-1) was 19.5%. The particle diameter of the fine particles obtained in the same manner as in Example 1 was measured and found to be 144 nm. Since the ratio of 90% particle size to 10% particle size was 2.66, it was confirmed that the particles were PIC dispersion fine particles having a narrow particle size distribution.

Example 4
100 mg of the polymer compound (I-2) obtained in Synthesis Example 2 was dissolved in 0.90 g of ion-exchanged water, and this was adjusted to pH 3 with 5N hydrochloric acid. An aqueous solution in which 100 mg of a red dye (CI Acid Red 249: manufactured by Kiwa Chemical Industry Co., Ltd.) was previously dissolved in 4.77 g of ion-exchanged water was added dropwise thereto. Here, the molar ratio of the anionic group in the yellow dye, which is a coloring compound, to the amine unit in the polymer compound (I-1) was 14.4%. The particle diameter of the fine particles obtained in the same manner as in Example 1 was measured and found to be 105 nm. Further, since the ratio of 90% particle size to 10% particle size was 1.45, it was confirmed that the particles were PIC dispersion fine particles having a particularly narrow particle size distribution.

Comparative Example 1
100 mg of branched polyethyleneimine (manufactured by Aldrich, molecular weight 25,000) was dissolved in 0.90 g of ion-exchanged water, and the pH was adjusted to 3 with 5 N hydrochloric acid. To this, an aqueous solution in which 100 mg of red dye (CI Acid Red No. 18: manufactured by Tokyo Chemical Industry Co., Ltd.) was previously dissolved in 4.77 g of ion-exchanged water was dropped. Here, the molar ratio of the anionic group in the red dye which is a coloring compound to the amine unit in the branched polyethyleneimine was 7.1%. When stirring of the solution was continued as it was, a viscous precipitate was soon generated from the solution mixture, and it did not become a dispersion.

Comparative Example 2
100 mg of branched polyethyleneimine (manufactured by Aldrich, molecular weight 25,000) was dissolved in 0.90 g of ion-exchanged water, and the pH was adjusted to 3 with 5 N hydrochloric acid. To this was added dropwise an aqueous solution in which 100 mg of yellow dye (CI Acid Yellow No. 17: manufactured by Kanto Chemical Co., Ltd.) was previously dissolved in 4.77 g of ion-exchanged water. Here, the molar ratio of the anionic group in the yellow dye as the coloring compound to the amine unit in the branched polyethyleneimine was 7.8%. When stirring of the solution was continued as it was, a viscous precipitate was soon generated from the solution mixture, and it did not become a dispersion.

Reference Example 1 [Synthesis of polymer compound composed of polyethylene glycol and polyethyleneimine]
Under a nitrogen atmosphere, 9.6 g of p-toluenesulfonic acid chloride was added to a mixed solution of 20.0 g (10.0 mmol) of methoxypolyethylene glycol [Mn = 2,000], 8.0 g (100.0 mmol) of pyridine and 20 ml of chloroform ( A chloroform (30 ml) solution containing 50.0 mmol) was added dropwise over 30 minutes while stirring with ice cooling. After completion of dropping, the mixture was further stirred at a bath temperature of 40 ° C. for 4 hours. After completion of the reaction, 50 ml of chloroform was added to dilute the reaction solution. Subsequently, after sequentially washing with 100 ml of 5% hydrochloric acid aqueous solution, 100 ml of saturated aqueous sodium hydrogen carbonate solution and 100 ml of saturated saline solution, it was dried over magnesium sulfate, filtered and concentrated under reduced pressure. The obtained solid was washed several times with hexane, filtered, and dried under reduced pressure at 80 ° C. to obtain 22.0 g of a tosylated product.

¹ H-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) measurement results are shown below.
¹ H-NMR (CDCl ₃ ) measurement result:
δ (ppm): 7.82 (d), 7.28 (d), 3.74-3.54 (bs), 3.41 (s), 2.40 (s)

  5.39 g (2.5 mmol) of a methoxypolyethylene glycol compound having a p-toluenesulfonyloxy group at the terminal synthesized above, polyethyleneimine (Epomin SP-200, manufactured by Nippon Shokubai Co., Ltd.) 8.0 g (0.8 mmol), 0.07 g of potassium carbonate and 50 ml of N, N-dimethylacetamide were placed in a flask and stirred at 100 ° C. for 6 hours under a nitrogen atmosphere. To the resulting reaction mixture, 200 ml of a mixed solution of ethyl acetate and hexane (V / V = 1/2) was added, and the mixture was vigorously stirred at room temperature (25 ° C.), and then the product solid was filtered. The solid was washed twice with 100 ml of a mixed solution of ethyl acetate and hexane (V / V = 1/2) and then dried under reduced pressure to obtain a polymer compound (I ′) composed of polyethylene glycol and polyethyleneimine. 12.7 g was obtained.

¹ H-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) measurement results are shown below.
¹ H-NMR (CDCl ₃ ) measurement result:
δ (ppm): 3.50 (s), 3.05 to 2.20 (m)

Comparative Example 3
100 mg of the polymer compound (I ′) composed of polyethylene glycol and polyethyleneimine produced in Reference Example 1 was dissolved in 2.0 g of ion-exchanged water, and this solution was cationized by adjusting the pH to 3 with 5N hydrochloric acid. did. In this solution, C.I. I. A solution prepared by dissolving 100 mg of Acid Red 18 in 5.00 g of ion exchange water at 70 ° C. was added. Here, the coloring compound C.I. I. The molar ratio of the anionic group in Acid Red 18 to the ethyleneimine unit (cation moiety) was 3.5%. When the particle size of the obtained particles was measured using FPAR1000 (Otsuka Electronics Co., Ltd.), the average particle size was 190 nm, and the ratio of 90% particle size to 10% particle size was 8.51. It was found that the particles had a wide particle size distribution.

Comparative Example 4
In Comparative Example 3, the coloring compound used was C.I. I. The same procedure as in Comparative Example 3 was conducted except that Acid Yellow 17 was used and the amount used was 6.5% (molar ratio). When the particle size of the obtained particles was measured using FPAR1000 (Otsuka Electronics Co., Ltd.), the average particle size was 200 nm, and the ratio of 90% particle size to 10% particle size was 7.10. It was found that the particles had a wide particle size distribution.

Test Example In Examples 1 to 4, a fine particle dispersion was taken out and dried under reduced pressure at 80 ° C. and 20 mmHg to obtain a powdered coloring material. When left in this state for about a week, returned to water again and subjected to ultrasonic treatment, a dispersion similar to the dispersion obtained in Examples 1 to 4 was obtained, and the redispersibility and storage stability were improved. It was confirmed that it was excellent.

Claims (10)

An aqueous solution comprising a polymer compound (I) having an epoxy resin residue (A) and a cationic hydrophilic polymer segment (B), and a coloring compound (II) having an anionic group Coloring material. The aqueous coloring material according to claim 1, wherein the epoxy resin residue (A) is a residue of a bisphenol A type epoxy resin or a naphthalene type tetrafunctional epoxy resin. The aqueous coloring material according to claim 1, wherein the cationic hydrophilic polymer segment (B) is a segment obtained by cationizing one or more polymers selected from the group consisting of polyethyleneimine, polyvinylamine, polyallylamine and polyvinylpyridine. The aqueous coloring material according to claim 1, wherein the cationic hydrophilic polymer segment (B) is a segment obtained by cationizing polyethyleneimine. The number average molecular weight of the epoxy resin residue of the polymer compound (I) is in the range of 300 to 10,000, and the degree of polymerization of the polymer constituting the cationic hydrophilic polymer segment (B) is 3 to 1, When the weight of the epoxy resin residue (A) in the polymer compound (I) is Wa and the weight of the cationic hydrophilic polymer segment (B) is Wb in the polymer compound (I), Wa / (Wa + Wb The aqueous coloring material according to claim 1, wherein 0.03 to 0.8. The molar ratio (anion / cation) of the anion in the coloring compound (II) having an anionic group to the cation in the cationic hydrophilic polymer segment (B) is 0.05 to 0.95. The aqueous coloring material according to 1. The aqueous coloring material according to claim 1, wherein the coloring compound (II) having an anionic group is a compound containing a sulfonic acid alkali metal salt or a carboxylic acid alkali metal salt moiety. The coloring compound (II) having an anionic group is selected from the group consisting of a fluorine atom, an alkylphenyl group which may have a substituent, and a phenoxyphenyl group which may have a substituent. The aqueous coloring material according to claim 1, which is a compound having one or more substituents. The aqueous coloring material according to any one of claims 1 to 8, wherein the epoxy resin residue (A) in the polymer compound (I) is in a colloidal form in which it is hydrophobically associated in an aqueous medium. A powdered coloring material obtained by drying the colloidal aqueous coloring material according to claim 9.